N′-[4-(2-Fur­yl)but-3-en-2-yl­idene]­iso­nicotino­hydrazide

Abstract

The mol­ecule of the title Schiff base compound, C₁₄H₁₃N₃O₂, is not perfectly planar; the furyl and pyridine rings are twisted with respect to each other along the C₄N₂C₂ organic chain, making a dihedral angle of 13.3 (1)°. The occurence of N—H⋯O hydrogen bonds builds up a chain developing parallel to the c axis.

Related literature

For background, see: Kahwa et al. (1986 ▶); Santos et al. (2001 ▶).

Experimental

Crystal data

• C₁₄H₁₃N₃O₂

• M _r = 255.27

• Monoclinic,

• a = 16.6325 (14) Å

• b = 9.3572 (8) Å

• c = 8.3554 (7) Å

• β = 100.912 (1)°

• V = 1276.87 (19) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 293 (2) K

• 0.25 × 0.23 × 0.16 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.965, T _max = 0.978

• 11728 measured reflections

• 3151 independent reflections

• 2124 reflections with I > 2σ(I)

• R _int = 0.026

Refinement

• R[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 0.132

• S = 1.03

• 3151 reflections

• 173 parameters

• H-atom parameters constrained

• Δρ_max = 0.20 e Å⁻³

• Δρ_min = −0.22 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2i	0.86	2.26	2.9289 (16)	134

Symmetry code: (i) .

supplementary crystallographic information

Comment

The chemistry of Schiff bases has attracted a great deal of interest in recent years. These compounds play an important role in the development of various proteins and enzymes(Kahwa et al., 1986; Santos et al., 2001). As part of our interest in the study of the coordination chemistry of Schiff bases, we have synthesized the title compound (I) and reported its cyrstal structure.

The molecule of the title compound is not perfectly planar, the furyl and the pyridine rings are twisted to each other along the C5/C6/C7/C8/N1/N2/C9 organic chain making a dihedral angle of 13.3 (1)°(Fig. 1). The organic chain is nearly planar with the largest deviation from the mean plane being 0.039 (1)Å at C7. The occurence of N-H···O hydrogen bonds builts up a chain developing parallel to the c axis (Fig. 2, Table 1).

Experimental

Pyridine-4-carboxylic acid hydrazide (1 mmol, 0.137 g) was dissolved in anhydrous methanol, H₂SO₄ (98% 0.5 ml) was added to this, the mixture was stirred for several minitutes at 351 K, furylideneacetone (1 mmol 0.136 g) in methanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized in dichloromethane, brown single crystals of (I) was obtained after 5 d.

Refinement

All H atoms were treated as riding on their parent atoms. Methyl H atoms were placed in calculated position with C—H=0.96Å and refined with U_iso(H)=1.5U_eq(C) Other H atoms were placed in calculated positions with C—H=0.93 Å, N—H=0.86Å and U_iso(H)=1.2U_eq(C,N).

Figures

Fig. 1.

Molecular view of (I) with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.

Fig. 2.

Partial packing view showing the N-H···O hydrogen bondings resulting in the formation of a chain parallel to the c axis. H atoms not involved in hydrogen bondings have been omitted for clarity. H bonds are shown as dashed lines. [Symmetry code: (i) x, -y+3/2, z+1/2]

Crystal data

C14H13N3O2	F(000) = 536
Mr = 255.27	Dx = 1.328 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2552 reflections
a = 16.6325 (14) Å	θ = 2.2–24.8°
b = 9.3572 (8) Å	µ = 0.09 mm−1
c = 8.3554 (7) Å	T = 293 K
β = 100.912 (1)°	Block, brown
V = 1276.87 (19) Å3	0.25 × 0.23 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3151 independent reflections
Radiation source: fine-focus sealed tube	2124 reflections with I > 2σ(I)
graphite	Rint = 0.026
ω scans	θmax = 28.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −22→20
Tmin = 0.965, Tmax = 0.978	k = −12→12
11728 measured reflections	l = −11→11

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0611P)2 + 0.1613P] where P = (Fo2 + 2Fc2)/3
3151 reflections	(Δ/σ)max = 0.005
173 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.34240 (10)	0.8729 (3)	0.0347 (2)	0.0765 (6)
H1	−0.3937	0.9084	0.0428	0.092*
C2	−0.33013 (10)	0.7542 (2)	−0.0421 (2)	0.0679 (5)
H2	−0.3700	0.6929	−0.0970	0.081*
C3	−0.24415 (10)	0.73836 (19)	−0.0245 (2)	0.0606 (4)
H3	−0.2168	0.6641	−0.0654	0.073*
C4	−0.20947 (9)	0.85094 (17)	0.06234 (19)	0.0510 (4)
C5	−0.12679 (9)	0.89496 (16)	0.12619 (19)	0.0496 (4)
H5	−0.1190	0.9739	0.1949	0.060*
C6	−0.06062 (8)	0.82982 (14)	0.09315 (18)	0.0454 (3)
H6	−0.0694	0.7556	0.0178	0.055*
C7	0.02404 (8)	0.86343 (14)	0.16352 (17)	0.0424 (3)
C8	0.04425 (9)	0.98435 (16)	0.2800 (2)	0.0547 (4)
H8A	0.0616	0.9475	0.3883	0.082*
H8B	−0.0033	1.0432	0.2765	0.082*
H8C	0.0875	1.0403	0.2503	0.082*
C9	0.21798 (8)	0.73017 (15)	0.13795 (17)	0.0439 (3)
C10	0.30344 (8)	0.77406 (15)	0.21280 (17)	0.0450 (3)
C11	0.32441 (9)	0.90777 (17)	0.2786 (2)	0.0540 (4)
H11	0.2842	0.9759	0.2829	0.065*
C12	0.40575 (10)	0.93870 (19)	0.3378 (2)	0.0653 (5)
H12	0.4186	1.0289	0.3821	0.078*
C13	0.44536 (11)	0.7198 (2)	0.2728 (3)	0.0838 (6)
H13	0.4868	0.6536	0.2703	0.101*
C14	0.36583 (10)	0.67795 (19)	0.2110 (2)	0.0651 (5)
H14	0.3547	0.5865	0.1689	0.078*
N1	0.07718 (7)	0.77927 (12)	0.11825 (15)	0.0466 (3)
N2	0.15805 (7)	0.80590 (12)	0.18733 (15)	0.0475 (3)
H2A	0.1701	0.8704	0.2613	0.057*
N3	0.46678 (9)	0.84786 (19)	0.3355 (2)	0.0772 (5)
O1	−0.26987 (7)	0.93681 (14)	0.10076 (15)	0.0705 (4)
O2	0.20525 (6)	0.63417 (12)	0.03656 (13)	0.0573 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0337 (9)	0.1172 (16)	0.0746 (13)	0.0063 (9)	0.0004 (8)	−0.0027 (12)
C2	0.0450 (10)	0.0840 (12)	0.0703 (12)	−0.0101 (9)	−0.0003 (8)	0.0038 (10)
C3	0.0477 (9)	0.0634 (9)	0.0681 (11)	−0.0004 (7)	0.0043 (8)	−0.0046 (8)
C4	0.0366 (8)	0.0627 (9)	0.0519 (9)	0.0068 (6)	0.0039 (6)	0.0025 (7)
C5	0.0401 (8)	0.0524 (8)	0.0533 (9)	0.0031 (6)	0.0012 (6)	−0.0001 (7)
C6	0.0390 (8)	0.0452 (7)	0.0489 (8)	0.0002 (6)	0.0002 (6)	0.0010 (6)
C7	0.0375 (7)	0.0415 (7)	0.0463 (8)	0.0010 (5)	0.0033 (6)	0.0039 (6)
C8	0.0425 (8)	0.0518 (8)	0.0649 (10)	0.0036 (6)	−0.0024 (7)	−0.0087 (7)
C9	0.0383 (7)	0.0502 (7)	0.0421 (8)	0.0003 (6)	0.0045 (6)	0.0005 (6)
C10	0.0357 (7)	0.0553 (8)	0.0434 (8)	−0.0004 (6)	0.0059 (6)	0.0005 (6)
C11	0.0382 (8)	0.0560 (9)	0.0693 (10)	−0.0045 (6)	0.0138 (7)	−0.0041 (8)
C12	0.0436 (9)	0.0708 (10)	0.0827 (12)	−0.0121 (8)	0.0147 (8)	−0.0144 (9)
C13	0.0405 (10)	0.0959 (14)	0.1109 (17)	0.0142 (9)	0.0039 (10)	−0.0275 (13)
C14	0.0449 (9)	0.0705 (10)	0.0769 (12)	0.0066 (8)	0.0039 (8)	−0.0174 (9)
N1	0.0329 (6)	0.0516 (6)	0.0526 (7)	−0.0027 (5)	0.0010 (5)	−0.0038 (5)
N2	0.0332 (6)	0.0528 (7)	0.0540 (7)	−0.0018 (5)	0.0021 (5)	−0.0111 (6)
N3	0.0382 (8)	0.0978 (12)	0.0931 (12)	−0.0041 (7)	0.0058 (7)	−0.0236 (9)
O1	0.0407 (6)	0.0913 (9)	0.0753 (8)	0.0138 (6)	0.0007 (5)	−0.0177 (7)
O2	0.0467 (6)	0.0676 (7)	0.0548 (7)	0.0016 (5)	0.0025 (5)	−0.0162 (5)

Geometric parameters (Å, °)

C1—C2	1.317 (3)	C8—H8C	0.9600
C1—O1	1.366 (2)	C9—O2	1.2253 (17)
C1—H1	0.9300	C9—N2	1.3496 (18)
C2—C3	1.417 (2)	C9—C10	1.4980 (19)
C2—H2	0.9300	C10—C14	1.375 (2)
C3—C4	1.346 (2)	C10—C11	1.385 (2)
C3—H3	0.9300	C11—C12	1.380 (2)
C4—O1	1.3711 (18)	C11—H11	0.9300
C4—C5	1.438 (2)	C12—N3	1.327 (2)
C5—C6	1.332 (2)	C12—H12	0.9300
C5—H5	0.9300	C13—N3	1.330 (2)
C6—C7	1.4540 (19)	C13—C14	1.382 (2)
C6—H6	0.9300	C13—H13	0.9300
C7—N1	1.2926 (18)	C14—H14	0.9300
C7—C8	1.489 (2)	N1—N2	1.3822 (15)
C8—H8A	0.9600	N2—H2A	0.8600
C8—H8B	0.9600
C2—C1—O1	111.08 (16)	H8B—C8—H8C	109.5
C2—C1—H1	124.5	O2—C9—N2	123.73 (13)
O1—C1—H1	124.5	O2—C9—C10	121.05 (13)
C1—C2—C3	106.49 (16)	N2—C9—C10	115.20 (12)
C1—C2—H2	126.8	C14—C10—C11	117.48 (14)
C3—C2—H2	126.8	C14—C10—C9	118.32 (14)
C4—C3—C2	107.16 (16)	C11—C10—C9	124.15 (13)
C4—C3—H3	126.4	C12—C11—C10	119.20 (15)
C2—C3—H3	126.4	C12—C11—H11	120.4
C3—C4—O1	109.08 (13)	C10—C11—H11	120.4
C3—C4—C5	134.95 (15)	N3—C12—C11	124.13 (16)
O1—C4—C5	115.91 (13)	N3—C12—H12	117.9
C6—C5—C4	124.18 (14)	C11—C12—H12	117.9
C6—C5—H5	117.9	N3—C13—C14	124.65 (17)
C4—C5—H5	117.9	N3—C13—H13	117.7
C5—C6—C7	126.31 (14)	C14—C13—H13	117.7
C5—C6—H6	116.8	C10—C14—C13	118.77 (16)
C7—C6—H6	116.8	C10—C14—H14	120.6
N1—C7—C6	114.42 (12)	C13—C14—H14	120.6
N1—C7—C8	124.89 (12)	C7—N1—N2	115.67 (11)
C6—C7—C8	120.68 (12)	C9—N2—N1	119.63 (12)
C7—C8—H8A	109.5	C9—N2—H2A	120.2
C7—C8—H8B	109.5	N1—N2—H2A	120.2
H8A—C8—H8B	109.5	C12—N3—C13	115.76 (15)
C7—C8—H8C	109.5	C1—O1—C4	106.18 (14)
H8A—C8—H8C	109.5

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2i	0.86	2.26	2.9289 (16)	134

Symmetry codes: (i) x, −y+3/2, z+1/2.